Azo dyestuffs and process of making same



45 lowing colour Patented Mar. 4,. 1930 water UNITED STATES, PATENT OFFICE HERMANN WAGNER, OF BAD-SODEN-ON-THE-TAUNUS, GERMANY, ASSTGNOR TO GEN- ERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., CORPORATION OF DELAWARE AZO DYESTUFFS AND PBOCESS OF MAKING SAME No Drawing. Original application filed February 12, 1923, Serial No. 618,710, and in Germany February 24, 1922. Divided and this application filed December 23, 1925. Serial No. 77,390.

great fast-ness, above all of a particularly striking fastness to kier-boiling and to light, I have found that dyestuffs of equally excellent fastness, particularly a striking fastness to kier-boiling, are produced by the combination of any diazo-compound with an arylamide of the 2.3-hydroxynaphthoic acid, halogenated in the aryl residue and substituted by an al l-or alkyl-oxy group in the para-position o the imino group.

.I have furthermore found that azo-dyes of equally good fastness are obtained by coupling halogenated diazo-components conarylamides of the 2.3-hydroxyn'aphthoic;acid not halogenated in the aryl' residue, but containing in the para position to the imino group an alkylor alkyloxy group.

Examples 1. The material is padded with a solution of 22,3 gr. 2.3 hydroxyn-aphthoic acid-p-anisi- 1 e v 60 com. caustic soda solution 22 B. 40 20 gr. para soap PN (i. e., the ammonium salt of sulfonated I'icinoleic acid) Made upto llitre. i v

It is then dried and printed with the foltaining an alkyl-or alkyloxy-group with' 14,1 gr. 4-chloro-2-toluidine are dissolved with 30 com. hydrochloric acid 22 B. and 200 com. hot water, cool well by adding 150 gr. ice. Thereupon add while well stirring 7,2 gr. sodium nitrite dissolved in com. water and make up with water to This diazo solution is thickened with 480 gr. tragacanth 60: 1000 (i. e., a solution of 60 parts by weight of tragacanth in 1000 parts by weight of water) and there are added before use 20 gr. sodium acetate cryst.

Thus a bright red tint of very good properties as to fastness is obtained.

The dyestufi' has. the following structural formula:

. CH3 N=N .2

3 4 I OH Cl CN I t it 2. The material is padded with a solution of:

OCH;

I Made up to 1 litre lowing colour:

It is then dried and printed with the fol- This diazo-solution is thickened with v48Ogr. tragacanth 60:1000 and there are 7 added before use 20 gr. sodium acetate cryst.

7 Thus a pure scarlet tint'of excellent properties as to fastness is obtained.

The dyestufl'has the following structural formula:

1 v N=N 2 5 c1 C-N on;

The diazo-solution obtained in the usual manner from-14,1 gr. of 5-chloro-2-toluidine is run, while stirring, into 'an'aqueous suspension of 33 gr. of 2.8 hydroxynaphthoic acid-panisidide prepared by dissolving it in caustic soda solution and precipitating with aid of acetic acid.-The dyestufi precipitates as bluish-red flakes, and is then filtered off,

' washed and dried. 1

223 2.3 hydroxynaphthoic acidp-anis idide in f The dyestufl has the structural formula:

1 I 2 on i 4. The material is padded with a solution of com. caustic soda solution I 20 gr. para soap PN Made up 1 litre It isthen dried-and printed with the-r51. lowing colour: A

15,7 gr. 4-chloro-2 -anisidine are dissolved v in 30 com. hydrochloric acid 22 B. and

200 com. hot water, cool by adding v 150 gr. ice. Add'while stirring a solution of Y .7 7,2 gr. sodium nitrite dissolved in 50 com. water and make up to' 500 gr. v This diazo-solution is thickened with 480 gr. tragacanth 60:1000 and there are 7 added before use 20 gr. sodium acetate cryst.

1 kg. Thusa red tint with a yellow hue of very good properties as to fastness is obtained.

The dyestuff has the structural formula;

v It i 7 5. The material is padded with a solution 0 v r 21 gr. 2.3hydroxynaphthoic acid-p-tolui dide in 60 com. caustic soda soluti0n22 Be. 20 gr. para soap PN Made up to 1 litre.

The dried material is printed with the following colour:

15, 7 gr 4-ch1oro-2-anisidine are dissolved 30 com. hydrochloric acid 22 B. and 200 com. hot water, cool by adding 150 gr. .ice. There is then added while stirring, a solution of 7,2 gr. sodium nitrite dissolved in 50 com. water and the whole is made up with water to 500 gr. v

This diazo-solution is thickened with I adde before use 20 gr; sodlum acetate'.

7i kg.

Thus a red tint with a blue hue of excellent properties as to fastness is obtained.

480 r. m acanth e'ouoooind there a gr. 4-chloro-2-anisidine is run into an aqueous suspension of 28 gr. 2.3 hydrOxynaphthoic acid-4-toluidide, prepared by dissolving it in caustic :soda

solution and precipitating with diluted acetic acid. The azo-dyestufi' precipitates in red flakes. It is filtered off, washed and dried.

The dyestufi has the structural formula: 00118:

7. The material is of:

padded with a solution 22,3 gr. 2.3 hydroxynaphthoic acid-4-anisidide.

Made up to 1 litre;

It is thendried and lowing colour:

ccm. caustic soda solution 22 B. gr. para soap PN printed with the folphenetidine ccm. hydrochloric acid 22 B. mix

well to a paste then cool with The yarn is ,im lowing preparation:

.gr. sodium phosphate and gr. sodium nitrite dissolyed in com. water thickened with 7 gr. tragacanth 60 1000 and add before make up The dyestufi has the structural formula:

pregnated with the fol- V The dyestuif has the structural formula: 10,55 gr. 2.3 hydroxynaphthoic acid-4-to- OCH v 20 com. caustic soda solution 34 B. N=N 30 com. sodium Turkey red oil 50% 5 500 com. hot water. Then make up with W i on Cl water to V 2 I 3 CH 1 litre.

The impregnated yarn is wrung out and dyed withthe following d'iazo solution:

3,44 gr. 4-chloro-2-phenetidine are mixed to a paste with i 5,2 ccm. hydrochloric acid 22 B. and 10 ccm. water, cool by adding 25 gr. ice, a'dd while stirring 1,44 gr. sodium nitrite in 5, 76 com. water and make up with water to 1 litre then add beforeiuse 4 gr. sodium acetate.

The dyestufl has the structural formula 0H Cl After dyeing the materialv is well washed and soaped. This application is a division of our application Ser. Nr. 618,710 of 12th February, 1923.

We claim:

1. As new products azo-dyestuffs of the 7 following constitution:

halogenated N=Naryl-R wherein R designates an alkyl or alkyloxy group. a

2. As new products, the azo-dyestufis oi the following constitution:

halogenated N=Naryl-R (I -N t 1!:

wherein R designates an alkylor alkyloxy group.

3. As new products, the azo dyestufis of the following constitution:

v am c-N H" A l 4. As a new product the azo-dyestufi of th following constitution:

y N= Cl I ON CH8 5.- Material .dy-ed' with the dyestufis of claim 1.

6. Material dyed with the dyestuffs of claim 2.

7. Material dyed with the dyestuffs: of claim 32' i 8. Material dyed with the dyestufl of claim 4.

' In testimony whereof, I afiix my signature.

v HERMANN WAGNER. 

